Limonite
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Limonite () is an
iron ore Iron ores are rocks and minerals from which metallic iron can be economically extracted. The ores are usually rich in iron oxides and vary in color from dark grey, bright yellow, or deep purple to rusty red. The iron is usually found in the ...
consisting of a mixture of
hydrate In chemistry, a hydrate is a substance that contains water or its constituent elements. The chemical state of the water varies widely between different classes of hydrates, some of which were so labeled before their chemical structure was understo ...
d
iron(III) oxide-hydroxide Iron(III) oxide-hydroxide or ferric oxyhydroxideA. L. Mackay (1960): "β-Ferric Oxyhydroxide". ''Mineralogical Magazine'' (''Journal of the Mineralogical Society''), volume 32, issue 250, pages 545-557. is the chemical compound of iron, oxygen ...
s in varying composition. The generic formula is frequently written as FeO(OH)·H2O, although this is not entirely accurate as the ratio of
oxide An oxide () is a chemical compound that contains at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– (molecular) ion. with oxygen in the oxidation state of −2. Most of the E ...
to
hydroxide Hydroxide is a diatomic anion with chemical formula OH−. It consists of an oxygen and hydrogen atom held together by a single covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. ...
can vary quite widely. Limonite is one of the three principal
iron ore Iron ores are rocks and minerals from which metallic iron can be economically extracted. The ores are usually rich in iron oxides and vary in color from dark grey, bright yellow, or deep purple to rusty red. The iron is usually found in the ...
s, the others being
hematite Hematite (), also spelled as haematite, is a common iron oxide compound with the formula, Fe2O3 and is widely found in rocks and soils. Hematite crystals belong to the rhombohedral lattice system which is designated the alpha polymorph of . ...
and
magnetite Magnetite is a mineral and one of the main iron ores, with the chemical formula Fe2+Fe3+2O4. It is one of the oxides of iron, and is ferrimagnetic; it is attracted to a magnet and can be magnetized to become a permanent magnet itself. With ...
, and has been mined for the production of
iron Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in ...
since at least 2500 BP.


Names

Limonite is named for the Greek word λειμών (/leː.mɔ̌ːn/), meaning "wet meadow", or λίμνη (/lím.nɛː/), meaning “marshy lake” as an allusion to its occurrence as '' bog iron ore'' in
meadow A meadow ( ) is an open habitat, or field, vegetated by grasses, herbs, and other non- woody plants. Trees or shrubs may sparsely populate meadows, as long as these areas maintain an open character. Meadows may be naturally occurring or arti ...
s and
marsh A marsh is a wetland that is dominated by herbaceous rather than woody plant species.Keddy, P.A. 2010. Wetland Ecology: Principles and Conservation (2nd edition). Cambridge University Press, Cambridge, UK. 497 p Marshes can often be found ...
es. In its brown form it is sometimes called brown hematite or brown iron ore.


Characteristics

Limonite is relatively dense with a
specific gravity Relative density, or specific gravity, is the ratio of the density (mass of a unit volume) of a substance to the density of a given reference material. Specific gravity for liquids is nearly always measured with respect to water at its dens ...
varying from 2.7 to 4.3.Northrop, Stuart A. (1959) "Limonite" ''Minerals of New Mexico'' (revised edition) University of New Mexico Press, Albuquerque, New Mexico, pp. 329–333, It is usually medium to dark yellowish brown in color. The streak of limonite on an unglazed porcelain plate is always yellowish brown, a character which distinguishes it from hematite with a red streak, or from magnetite with a black streak. The
hardness In materials science, hardness (antonym: softness) is a measure of the resistance to localized plastic deformation induced by either mechanical indentation or abrasion. In general, different materials differ in their hardness; for example hard ...
is quite variable, ranging from 1 to 5. In thin section it appears as red, yellow, or brown and has a high index of refraction, 2.0 - 2.4. Limonite minerals are strongly birefringent, but grain sizes are usually too small for this to be detectable. Although originally defined as a single mineral, limonite is now recognized as a field term for a mixture of related
hydrate In chemistry, a hydrate is a substance that contains water or its constituent elements. The chemical state of the water varies widely between different classes of hydrates, some of which were so labeled before their chemical structure was understo ...
d
iron oxide Iron oxides are chemical compounds composed of iron and oxygen. Several iron oxides are recognized. All are black magnetic solids. Often they are non-stoichiometric. Oxyhydroxides are a related class of compounds, perhaps the best known of wh ...
minerals, among them goethite,
lepidocrocite Lepidocrocite (γ-FeO(OH)), also called esmeraldite or hydrohematite, is an iron oxide-hydroxide mineral. Lepidocrocite has an orthorhombic crystal structure, a hardness of 5, specific gravity of 4, a submetallic luster and a yellow-brown ...
,
akaganeite Akaganeite, also written as the deprecated Akaganéite,Ernst A.J. Burke (2008):Tidying up Mineral Names: an IMA-CNMNC Scheme for Suffixes, Hyphens and Diacritical marks. ''Mineralogical Record'', volume 39, issue 2. is a chloride-containing ir ...
, and
jarosite Jarosite is a basic hydrous sulfate of potassium and ferric iron (Fe-III) with a chemical formula of KFe3(SO4)2(OH)6. This sulfate mineral is formed in ore deposits by the oxidation of iron sulfides. Jarosite is often produced as a byproduct d ...
. Determination of the precise mineral composition is practical only with X-ray diffraction techniques. Individual minerals in limonite may form
crystal A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macro ...
s, but limonite does not, although specimens may show a fibrous or
microcrystalline A microcrystalline material is a crystallized substance or rock that contains small crystals visible only through microscopic examination. There is little agreement on the range of crystal sizes that should be regarded as microcrystalline, but the ...
structure, and limonite often occurs in concretionary forms or in compact and earthy masses; sometimes mammillary, botryoidal, reniform or stalactitic. Because of its amorphous nature, and occurrence in hydrated areas limonite often presents as a clay or mudstone. However, there are limonite
pseudomorph In mineralogy, a pseudomorph is a mineral or mineral compound that appears in an atypical form ( crystal system), resulting from a substitution process in which the appearance and dimensions remain constant, but the original mineral is replaced ...
s after other minerals such as
pyrite The mineral pyrite (), or iron pyrite, also known as fool's gold, is an iron sulfide with the chemical formula Iron, FeSulfur, S2 (iron (II) disulfide). Pyrite is the most abundant sulfide mineral. Pyrite's metallic Luster (mineralogy), lust ...
. This means that chemical weathering transforms the crystals of pyrite into limonite by hydrating the molecules, but the external shape of the pyrite crystal remains. Limonite pseudomorphs have also been formed from other iron oxides, hematite and magnetite; from the carbonate siderite and from iron rich silicates such as almandine garnets. File:La Palma Limonit.jpg, Limonite deposited from mine runoff File:Galena Limonite.jpg, Galena and limonite File:GranadaEZ.jpg, Limonite pseudomorphs after garnet


Formation

Limonite usually forms from the hydration of hematite and magnetite, from the oxidation and hydration of iron rich sulfide minerals, and chemical weathering of other iron rich minerals such as
olivine The mineral olivine () is a magnesium iron silicate with the chemical formula . It is a type of nesosilicate or orthosilicate. The primary component of the Earth's upper mantle, it is a common mineral in Earth's subsurface, but weathers qui ...
,
pyroxene The pyroxenes (commonly abbreviated to ''Px'') are a group of important rock-forming inosilicate minerals found in many igneous and metamorphic rocks. Pyroxenes have the general formula , where X represents calcium (Ca), sodium (Na), iron (Fe I ...
,
amphibole Amphibole () is a group of inosilicate minerals, forming prism or needlelike crystals, composed of double chain tetrahedra, linked at the vertices and generally containing ions of iron and/or magnesium in their structures. Its IMA symbol is ...
, and
biotite Biotite is a common group of phyllosilicate minerals within the mica group, with the approximate chemical formula . It is primarily a solid-solution series between the iron- endmember annite, and the magnesium-endmember phlogopite; more ...
. It is often the major iron component in lateritic soils, and limonite laterite ores are a source of nickel and potentially cobalt and other valuable metals, present as trace elements. It is often deposited in run-off streams from mining operations.


Uses

Nickel-rich limonite ores represent the largest reserves of nickel. Such minerals are classified as
lateritic nickel ore deposits Lateritic nickel ore deposits are surficial, weathered rinds formed on ultramafic rocks. They account for 73% of the continental world nickel resources and will be in the future the dominant source for the mining of nickel. Genesis and types of ...
. One of the first uses was as a
pigment A pigment is a colored material that is completely or nearly insoluble in water. In contrast, dyes are typically soluble, at least at some stage in their use. Generally dyes are often organic compounds whereas pigments are often inorganic compou ...
. The yellow form produced yellow
ochre Ochre ( ; , ), or ocher in American English, is a natural clay earth pigment, a mixture of ferric oxide and varying amounts of clay and sand. It ranges in colour from yellow to deep orange or brown. It is also the name of the colours produced ...
for which
Cyprus Cyprus ; tr, Kıbrıs (), officially the Republic of Cyprus,, , lit: Republic of Cyprus is an island country located south of the Anatolian Peninsula in the eastern Mediterranean Sea. Its continental position is disputed; while it is ...
was famous, while the darker forms produced more earthy tones. Roasting the limonite changed it partially to hematite, producing red ochres, burnt umbers and siennas. Bog iron ore and limonite mudstones are mined as a source of iron, although commercial mining of them has ceased in the United States. ''Iron caps'' or gossans of siliceous iron oxide typically form as the result of intensive
oxidation Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or ...
of
sulfide Sulfide (British English also sulphide) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. ''Sulfide'' also refers to chemical compounds la ...
ore deposits.Brown, G. Chester (1915) ''Mines and mineral resources of Shasta county, Siskiyou county, Trinity county'' California State Mining Bureau, California State Printing Office, Sacramento, California
pages 15–16
These gossans were used by prospectors as guides to buried ore. In addition the oxidation of those sulfide deposits which contained
gold Gold is a chemical element with the symbol Au (from la, aurum) and atomic number 79. This makes it one of the higher atomic number elements that occur naturally. It is a bright, slightly orange-yellow, dense, soft, malleable, and ductile ...
, often resulted in the concentration of gold in the iron oxide and quartz of the gossans. Goldbearing limonite gossans were productively mined in the Shasta County, California mining district. Similar deposits were mined near Rio Tinto in
Spain , image_flag = Bandera de España.svg , image_coat = Escudo de España (mazonado).svg , national_motto = '' Plus ultra'' (Latin)(English: "Further Beyond") , national_anthem = (English: "Royal March") , ...
and Mount Morgan in
Australia Australia, officially the Commonwealth of Australia, is a sovereign country comprising the mainland of the Australian continent, the island of Tasmania, and numerous smaller islands. With an area of , Australia is the largest country by ...
. In the Dahlonega gold belt in Lumpkin County, Georgia gold was mined from limonite-rich lateritic or
saprolite Saprolite is a chemically weathered rock. Saprolites form in the lower zones of soil profiles and represent deep weathering of the bedrock surface. In most outcrops its color comes from ferric compounds. Deeply weathered profiles are widesprea ...
soil. The gold of the primary veins was concentrated into the limonites of the deeply weathered rocks. In another example the deeply weathered iron formations of
Brazil Brazil ( pt, Brasil; ), officially the Federative Republic of Brazil (Portuguese: ), is the largest country in both South America and Latin America. At and with over 217 million people, Brazil is the world's fifth-largest country by area ...
served to concentrate gold with the limonite of the resulting soils.


History

While the first iron ore was likely meteoric iron, and hematite was far easier to
smelt Smelt may refer to: * Smelting, chemical process * The common name of various fish: ** Smelt (fish), a family of small fish, Osmeridae ** Australian smelt in the family Retropinnidae and species ''Retropinna semoni'' ** Big-scale sand smelt ''A ...
, in Africa, where the first evidence of iron metallurgy occurs, limonite is the most prevalent iron ore. Before smelting, as the ore was heated and the water driven off, more and more of the limonite was converted to hematite. The ore was then pounded as it was heated above 1250 °C, at which temperature the metallic iron begins sticking together and non-metallic impurities are thrown off as sparks. Complex systems developed, notably in Tanzania, to process limonite. Nonetheless, hematite and magnetite remained the ores of choice when smelting was by
bloomeries A bloomery is a type of metallurgical furnace once used widely for smelting iron from its oxides. The bloomery was the earliest form of smelter capable of smelting iron. Bloomeries produce a porous mass of iron and slag called a ''bloom''. ...
, and it was only with the development of
blast furnace A blast furnace is a type of metallurgical furnace used for smelting to produce industrial metals, generally pig iron, but also others such as lead or copper. ''Blast'' refers to the combustion air being "forced" or supplied above atmospheri ...
s in the 1st century BCE in China and about 1150 CE in Europe, that the brown iron ore of limonite could be used to best advantage. Limonite was one of the earliest materials used as a pigment by humans, and can be seen in Neolithic
cave painting In archaeology, Cave paintings are a type of parietal art (which category also includes petroglyphs, or engravings), found on the wall or ceilings of caves. The term usually implies prehistoric origin, and the oldest known are more than 40,000 ye ...
s and pictographs.Wilford, John Noble (13 October 2011
"In African Cave, Signs of an Ancient Paint Factory"
''The New York Times''; hardcopy published 14 October 2011 under title "African Cave, Ancient Paint Factory Pushes Human Symbolic Thought ‘Far Back’" New York edition page A-14; archived by WebCitebr>page 1
an

on 11 March 2012


See also

* Ore genesis


Notes


External links

{{Commons, Limonite
Mineral galleries
Iron ores Rocks